Terminal-depolarizer unit for primary cells



April 25, 1961 R. A. WARREN ETAL TERMINALDEPOLARIZER UNIT FOR PRIMARY CELLS Filed June 2e, 195s Q 9 m/ Qm 1423 7 2 l uxv l United States TERMINAL-DEPOLARIZER PRIMARY CELLS Robert A. warren and Milton E. Wilke, Freeport, Iii., assigiiors, by mesne assignments, to Servel, Inc., Evansville, Ind., a corporation of Delaware Filed June 26, 1958, Ser. No. 744,772 16 Claims. (CL 13G-136) UNIT FOR therewith, and of the method.

Such cells an amalgamated zinc anode, a mercuric oxide cathode compressed into a metallic cup-form terminal, an alkaline electrolyte substantially immobilized in an absorbent separator such as Webril, and a metallic container for the cell.

Because mercuric oxide itself has poor electrical conductivity, a conductive material such as graphite is generallydispersed thereinto in preparing the cathode coinsufficiently large depolarizer cathode. As a result, a compressed depolarizer pellet is first formed outside the terminal cup and subsequently inserted thereinto. However, if the compressed cathode pellet o suiliciently good electrical contact is`iiot pellet into the cup. This method is objectionable in `several` respects, however. `When the pellet is compressed o into `the cup, a small amount of the depolarizer material is caused to be extruded up the sides.` This extruded is merely placed i aan' o material must be removed prior to cell assembly. Aiil otheruobjection is that expensive equipmentis required for the latter compression step, adding considerably to `the cost of manufacture of the cells.

method "for the constriiction of the assemblywhich?A o does not require expensiveoequipment.

It is still further an object to provide terminal-detweeii saidcathode and said terminal. o o `Qther` obiects and improvements ofthe invention will become f apparent" from fthe following fronithedrawiiigs o Inthe drawings?" 1 Fig. 1 is a vcross-sectional view of an alkaline cell coni description Aand such assteel or deep-drawing steel has developed duringoperation of the `cell. is of a smaller` diameter and is somewhat 2,981,782 Patented Apr. 25, 1961 taining a depolarizer-terminal assembly according to the invention;

Fig. 2 is a cross-sectional view of the terminal-depolar- V for example of a conductive finely The adhesive `'I'he comthe pellet and firmly bonded to each other by a position is then allowed to cool, causing terminal to become means of a layer of composition of the invention.

Attached to the outer cup 1 bymeans of a rivet 8 or i other equivalent `fastening means are the sealing disk 9,

` The cups land of a suitable rigid material `nickel-plated steel. A .O15 inch thick be suitable. This material is suiciently thick to withstand the gas pressure The inner cup 2 shorter in height A negative terminal, with the louter cup, whichisV 4in electrical contact withthe` positive i ing of the cell.-

terminal, as such` contact would `result in the short-circuit- The depolarizer-terminal unit` maybe assembled in any one of a number of different ways. The conductive composition may be first placed in the terminal and the pellet placed jthereover. o A. o iiisuflicientfamont tomelt the Wax]l and render the' comi positionwflowable. A

position allowed tol Heatis'then applied tothe cup The heatis removediandithe comcool and harden. Alternatively, the

wax may iirst be melted in the cup and the pellet inserted, and the composition then cooled. In still another method, molten wax may be placed in the terminal cup, and the pellet placed over the wax composition. The conductive wax may also be melted on thebottomfof the-pellet, yallowed to harden and the pellet placed in the cup. To insure a low resistance bond, pressure should preferably be applied to the pellet to hold it against the'terminal cup Vuntil the molten composition lhas hardened. Where *silver upon their surfaces.

f a lower order of depolarizer. permeable are not nearly as conductive adhesives other than wax are used, suitable methods may bel used to harden them.

In the preferred form of the invention the pellet should be provided with a somewhat smaller diameter than the diameter of the cup. VWhen the pellet is pressed into the cup, molten wax creeps around the side of the pellet, and provides additional adhesion between the pellet side `and the cup side. Whenthe wax is allowed to solidify, the pellet is firmly held in the cup withrgood electrical contact enhanced by the additional adhesive Contact surface between the side of the pellet and the inner side of the can. Where the pellet has the same diameter as the terminal cup, however, the adhesive layer willbe limited to the bottom of the cup.

The present conductive adhesive composition comprises an electrically conductive finely divided material dispersed in 'an adhesive binder such as wax or any other suitable adhesive. The finely divided material .must be of such nature that it maintains its lsurface conductive even though exposed to the corrosive action of the air. One such suitable material is silver powder, since silver oxide formed upon exposure of the particles to air is also a good conduct-or. A suitable composition comprises silver powder dispersed in a wax, as disclosed in U.S. Patent No. 2,702,757. l tained therein, silver powder which has been Vpreferably rolled in a mill to increase its apparent density, is mixed together with a molten wax such as microcrystalline wax until a uniform composition is attained. The resulting composition is highly conductive, has a relatively low melting point, and has excellent adhesive properties.

Copper powder alone is' not a suitable material since the copper oxide formed on the surface upon exposure to air is a poor conductor. `However, if copper powder is first plated with silver, as disclosed in U.S. Patent No. 2,771,380, thecomposition retains its excellent conductivity even when exposed to air. According to the disclosure of this patent, copper powder is first dry mixed with discreet particles'of crystalline hydrated sodium sulfate, and the mixture then immersed in an aqueous cyanide silver plating bath. As a result of this process the dis- ;creet copper particles acquire an immersion plating of Y The silver plated copper powder may then be used in the same manner as the silver particles in the method described above to forni theconcluctive-A ladhesive composition. Other metal' powders which may be plated with silver to render their 'surfaces conductive may also be used. Although similar compositions containing graphite as the conductive material as those containing silver or silver plated metals, they sometimes may be used when conductivity is tolerable, such as in the case when the resulting batteries are^to be subjected only to a very low current drain. p

The depolarizing cathode 3is'comp`osedof a vmixture lof a powdered oxygen-yielding substancesuch as rnercuricy oxide, mercurous oxide, silver oxide, silver peroxide, cuprous oxide, manganese dioxide, nickelous oxide, `or other readily reducible oxygen-yielding compounds or mixtures thereof, as micronized graphite.

The depolarizer'pellet 'is cornpressed to a thickness lpreferably aboutonefthird that of the height of the inner can 2.

The barrierdisk l restsupon the top-surface-of the materialwhich is substantially resistant to the action ofthe' electrolyte, such aspprarcl'imentV paper,

and a suitable conductive substance such,

It is madey of a suitable liquidand ion" Y such as zinc.

i such as steel which porous vinyl resin, vinylidene resin, or 'compressed magnesium oxide or magnesium silicate. The barrier disk prevents particles of the depolorizer, graphite or reduced mercury from migrating through the cell and causing electrical short-circuiting. It preferably has an initial diameter somewhat larger than that of the depolarizer so that it tits'tightly in place in the cell.

The electrolyte-receptive separator 5 presses against the barrier disk and is composed ofva suitable, porous, absorbent, electrolyte-resistant material such as wood or cotton fibers, as for example'po-rous absorbent paper or absorbent cotton. A preferred material is webril, a fibrous cellulose in the form of a pad. vIn order to have suicient thickness, the separatorV may be composed of several pads in stacked relationship. It is maintained under compression between the anode 6 and the barrier disk 4 and contains the major portion of the cell electrolyte absorbed therein. Alternatively, a gelled electrolyte may be used.

The electrolyte is generally an aqueous solution of sodium, potassium, or lithium hydroxide, or a mixture thereof. It may additionally contain dissolved therein an oxide such as zinc oxide or aluminum oxide to inhibit attack by the electrolyte upon the anode during the period when the cell is not in operation.

The anode is composed of an electronegative .metal In order that it may have a high surface area and readily absorb the cell electrolyte, it is preferably vmade by compressing .zinc powder into a pellet. Prior to formation of the anode the zinc powder isprefthe cell electrolyte .when Ythe cell is not in operation. The anode is held in pressure contact against 'the separator by the rivet head 8a.

The rivet 8 is made of any suitable conducting material is sufficiently malleable so that its end may be upset. The rivet head preferably has a rather large surface area for engagement with the anode, and also for forming an airtight seal with the sealing disk; it ispreferably coated with a metal such as tin, zinc, or nickel to prevent chemical action by the electrolyte thereon. Y

The sealing disk 9 is composed of a resilient,-yieldable material such as neoprene polyethylene, modified polystyrene vinyl plastic vulcanized fiber etc. In a preferred embodimentas illustrated in Figure 1 the sealing disk is of a laminated construction having'an upper layer 9a serves to insulate mined amount of the which is less resilient and semi-rigid Vsuch as a laminated phenolic resin sheet or melamine resin sheet reinforced with fiber glass and one or more lower layers of resilient material 9b. If only one resilient layer is used, the disk should be arranged so that the resilient layer Vis in contact with the lip of the inner cup `and the rivet head, the semi-rigid disk serving as a backingv to Vimpart stiffness. If more than one resilient layer is used, one should be afxed to each surface of the less resilient layer. V,The sealing disk has a diameter substantially the sameV as the inside of the outer cup and `serves as a closure for the inner cup which contains the activefcell materials. It is maintained inV pressure rcontact ,with Athe lip of the inner cup when the lip of the outer `cup is crimpedover the bottom ofthe inner ,The terminal diskV or ing material'such cup in Vthe assembly ofthecell. washer 11 may be of a conductas steel or plated steel. The `disk`10 the outer cuprfrom the terminal disk.

The negative terminalll, insulatingdisk` l1() and sealing disk 9 maybe assembled asa singlefur'iit if desired,

the terminal-depolarizerA unit, ,predetere conductive composition such as finewax binder is placed in the bottom To produce ly divided silver in a s of the inner cup 2 and the pellet placed over ,the wax until the molten Wax composition. 'The cup 2 'isplaced on .aheated surface has Vformed intimate vcontact with the depolarizerpelletand the cup,

the surface of both The cup is then placed on a cool surface and the wax composition allowed to harden.

The cell is assembled by placing the active chemical cell elements in the inner cup and adding the required amount of electrolyte. The cell is completed by placing the outer cup assembly over the inner cup 2 and the absorbent band 12. Sealing of the cell is accomplished by crimping the lip of the outer cup 1 over the bottom of the inner cup 2. This provides an axial clamping force which compresses the sealing disk against the inner cup lip to maintain a good air-tight seal.

The positive terminal-depolarizer pellet unit produced according to the present invention and the cell containing the unit have several advantages over those constructed according to the art. First, the need for machinery for providing the necessary high compression for compressing the pellet into the cup is obviated. Second, lateral extrusion of the depolarizer mix during the compression step is avoided. Third, the pellet is instantly bonded to the cup by means of the conductive composition, insuring a strongly bonded highly conductive electrical connection.

We claim:

1. A method for the production of a terminal-depolarizer unit for primary cells comprised of a metallic terminal bonded to a preformed compressed depolarizer pellet, said method comprising interposing a molten film of a conductive compositions consisting essentially of an electrically conductive finely divided material in a wax binder at an interface between said terminal and said depolarizer pellet, and cooling said composition to form an adherent'conductive bond between said terminal and said pellet without deforming said pellet.

2. A method according to claim 1 wherein said finely divided material is silver.

3. A method according to claim 1 wherein said finely divided material is comprised of copper particles having an adherent silver coating thereon. t

4. A method for the production of a terminal-depolarizer unit for primary cells comprised of a metallic cup containing a preformed compressed depolarizer pellet bonded thereto, said method comprising interposing a molten film of an electrically conductive composition consisting essentially of a conductive finely divided metal dispersed in a wax binder at an interface between said cup and said depolarizer pellet, and cooling said composition to form an adherent conductive bond between said cup and said pellet without deforming said pellet.

5. A method for the production of a terminal-depolarizer unit for primary cells comprised of a metallic cup containing a preformed compressed depolarizer pellet bonded thereto, said method comprising providing a molten film of an electrically conductive composition consisting essentially of a conductive finely divided metal in a wax binder in the bottom of said cup, placing said pellet in said cup, adherent conductive bond between said cup and said pellet without deforming said pellet.

6. A method for the production of a terminal-depolarizer unit for primary cells comprised of a metallic cup containing a preformed compressed depolarizer pellet bonded thereto, said method comprising placing an electrically conductive composition consisting essentially of finely divided metal dispersed in a wax binder in said cup, inserting said depolarizer pellet in said cup over said composition, heating said cup to provide a molten and cooling said composition to form an` said pellet, said composition consisting essentially of a conductive nely divided material in a wax binder.

8. A terminal-depolarizer unit according to claim 7 wherein said conductive adhesive composition consists essentially of a conductive finely divided material in a wax binder.

9. A terminal-depolarizer unit for primary cells comprising a metallic cup, a preformed compressed depolarizer pellet, and a film of an electrically conductive adhesive composition interposed at the interface and forming an adherent conductive bond between said cup and said pellet, said conductive composition consisting essentially of a conductive finely divided material in a wax binder.

10. A terminal-depolarizer unit for primary cells comprising a metallic cup, a preformed compressed depolarizer pellet, and a lm of an electrically conductive adhesive composition interposed at the interface forming an 'adherent conductive bond between said terminal and said pellet, said composition consisting essentially of a conductive finely divided metal in a wax binder.

11. A terminal-depolarizer unit according to claim 10 wherein said finely divided metal is silver.

12. A terminal-depolarizer unit according to claim 10 wherein said finely divided metal comprises a conductive metal having an adherent silver coating thereon.

13. A terminal-depolarizer unit according to claim 10 wherein said finely divided metal comprises copper having an adherent silver coating thereon.

14. In a primary alkaline cell comprising a cell closure having a positive terminal and a negative terminal, active cell elements including an anode, a preformed compressed depolarizer pellet, a non-conductive liquid-absorbent separator, and an alkaline electrolyte contained in said separator, the improvement which comprises a bonded positive terminal-depolarizer unit comprised 4of said positive terminal, said compressed depolarizer pellet, and a film of an electrically conductive adhesive composition interposed at the interface and forming an adherent conductive bond between said terminal and said pellet, said composition consisting essentially of a conductive finely divided metal in a wax binder.

15. An alkaline primary cell according to claim 14 wherein said finely divided metal is silver.

16. An alkaline primary cell according to claim 14 wherein said finely divided metal comprises copper particles having an adherent coating of silver thereon.

References Cited in the file of this patent UNITED STATES PATENTS 

